JPH10207116A - Toner for electrostatic latent image developer, its manufacture, electrostatic latent image developer and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance oilless fixability without need to supply a fixing system with an oil, filming performance, and toner powder characteristics using a wax, and moreover, to exhibit high transferability necessary for color images together with the above-mentioned various characteristics to high grade. SOLUTION: The toner to be used for the electrostatic latent image developer composed of a binder resin and a colorant, and the toner contains the wax in an amount of 0.1-40 weight % and the wax disclosed on the surfaces of the toner trains in an amount of 1-10 weight %, and the wax dispersed in the toner having a number average dispersed particle diameter of of 0.1-2μm. This toner is obtained by dissolving or dispersing each material of the resin and the colorant and the wax in an organic solvent to form an oil phase mixture and granulating it and subjecting the obtained granules to suspension polymerization. It is preferred to finely pulverize the wax in advance, especially, into the forms of thin flakes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for an electrostatic latent image developer used in an electrophotographic process or the like, a method for producing the same, a two-component electrostatic latent image developer using the toner, and a developer for the same. The present invention relates to an image forming method used.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
As described in US Pat. No. 7,691 and Japanese Patent Publication No. 42-23910 (U.S. Pat. No. 3,666,363), many methods are known. Exposure step for forming an electric latent image on the photoreceptor layer using a conductive material using various means, development using toner, transfer of toner to a recording material such as paper, and heating of the toner image , A process of fixing the recording material by pressure, heat pressure or solvent vapor, and a process of removing the toner remaining on the photoreceptor layer.

Recently, there has been an increasing demand for making inexpensive and compact copiers or printers using electrophotography. In designing such copiers or printers, how much toner can be used with low power consumption. It is important to simplify the fixing method as well as to fix.

As a means for fusing and fixing a toner to paper, a fixing method using a hot roll is most commonly used at present. In a monochrome copier or printer machine, a system that does not require oil supply to the heat roll is generally used, but for color toner, oil is still supplied to the roll to prevent offset to the heat roll. Means are essential, and these are the hindrance factors in designing a small and inexpensive system. The reason for this is
In a full-color system using a cyan, yellow, or magenta toner among color toners, and in which it is necessary to obtain a clear color multicolor image, it is necessary to sufficiently heat and melt each toner layer. This is because the fixing temperature of the roll usually needs to be sufficiently raised to a temperature higher than the temperature at which the paper is fixed.

Further, as a toner for electrostatic development used in the field of electrophotography, recently, a resin which melts sharply at the time of fixing and has a smooth image surface, that is, a resin having a low molecular weight and a narrow molecular weight distribution is used. However, polyesters having sufficient flexibility even when the molecular weight is reduced are often used. However, such a polyester resin for a color toner having a small internal cohesive force is hard to be peeled off from a roll at the time of melting, and it has been difficult to use a color toner using the polyester resin and a fixing method that does not require oil application.

In order to solve such a problem, see, for example,
JP-3304, JP-A-52-3305, JP-A-57-52574, JP-A-61-138259
JP, JP-A-56-87051, JP-A-63-87051
As described in JP-A-188158, there is an approach of using a toner to which a release agent is added and facilitating peeling from a roll, and has been widely studied. However, although the toner containing the release agent therein has achieved some success in terms of roll releasability, it has not always been satisfactory in all toner characteristics. One of the reasons is that it is difficult to control the amount of the release agent contained in the toner and the amount of the release agent present on the toner surface to an optimum state. In order to satisfy this, the amount of the release agent added to the toner is desirably 1 to 10% by weight, and the effect of the release is increased as the amount of the release agent is increased. The toner has a problem that the powder fluidity and the thermal cohesion of the toner are deteriorated by the addition amount of only 1 to 3% by weight. This is because the wax generally used as a release agent is exposed at a high concentration together with the pigment on the toner surface, which is the fracture surface of the pulverization. In addition, the surface wax partially melts and spreads due to the collision of particles in a pulverizing device or a classifying device in the production process or frictional heat with the device wall, and further covers the toner surface. Japanese Patent Application Laid-Open No. 02-87159 discloses that a mechanical impact force is applied to a kneaded and pulverized toner containing a wax to determine the amount of wax on the surface of the spherical toner by ESCA. Usually 1 to
The proportion of the wax present on the surface of the kneaded and pulverized toner to which 10% by weight of the wax is added is about 30 to 50% by weight.
Furthermore, the surface of the photoconductor and the surface of the carrier are contaminated,
There has been a problem that fluctuations in development characteristics are caused. In addition, there is a problem that the adhesive force between the photoreceptor and the intermediate transfer member is increased, so that the transfer efficiency of the toner is low. .

[0007] In order to overcome such disadvantages of the toner to which the wax is added, a novel toner production method has been proposed. For example, JP-A-60-222868, JP-A-61-114247, and JP-A-59-162562
Is a toner having a capsule-type structure as disclosed in Japanese Patent Application Laid-Open No. H10-209,794. Such a toner having a capsule structure can reduce the proportion of low molecular weight components such as wax exposed on the surface to about 0 to 1% by weight, and relates to the above-described blocking property, filming property, and developing property. There are relatively few issues. However, a toner completely free of such a surface wax often cannot always achieve sufficient roll release properties. To prevent offset to the roll, a release layer (Wea) made of molten wax or the like is placed between the toner melted in the hot roll fixing nip and the roll surface.
k Boundary Layer) instantaneously,
Although direct contact with the toner resin must be prevented in an extremely short time, if the wax is completely contained, a delay occurs in which the molten wax diffuses to the interface inside the binder resin, and a weak state occurs. Boundary layers cannot be formed sufficiently. Further, when a color image is produced with such a capsule type toner having a hard shell on the surface, a higher temperature is generally required to completely melt the toner image. The releasability from the roll was more difficult.

Another method for producing a toner is to form oil droplets of a monomer composition or a toner composition in a dispersion medium having a large polarity called water, so that a component having a polar group contained in the oil droplets is formed. A so-called pseudo-capsule structure, which makes it easier to exist in the surface phase portion, which is the interface with the aqueous phase, and makes it difficult for nonpolar components to be present in the surface layer portion. A typical example is a suspension polymerization method toner described in JP-B-36-10231. The toner produced by the wet production method can control the amount of the wax present on the toner surface and the amount of the wax inside the toner within a range in which the blocking resistance and the oilless fixing property can be relatively compatible, by utilizing the characteristics of the production method. . However, in the above-mentioned suspension polymerization method toner, as the polymerization proceeds, the phase separation between the non-polar wax component and the polymer mainly composed of a polar monomer is promoted, and the pseudo-capsule structure described above is taken. However, such separation during the polymerization process tends to fluctuate depending on the composition of the monomer and the conditions at the time of polymerization, and it has been difficult to perform stable structural control industrially. JP-A-05-88409
The publication discloses that wax cannot be present on the surface up to a depth of 0.15 times the particle size, which has the same problem as the above-mentioned capsule type toner. Furthermore, the polymerizable monomer composition of the resin to be a toner is limited to polymerizable monomers capable of solution polymerization, such as styrene and its derivatives and α-methylene aliphatic monocarboxylic acid esters. As described above, there is also a problem that it is difficult to use polyester required for a color toner as a toner resin.

The problem that there is a limitation in selecting a resin material for the toner is, of course, the above-described kneading and pulverizing method.
That is, as a resin for toner, it must be sufficiently brittle and must be able to be finely pulverized by an ordinary fine pulverizer, and it is necessary to make the resin brittle. The problems are that the particle size distribution is widened and coarse particles are mixed.

[0010] From the above, a new toner structure which can be widely selected as a resin for a toner, and which satisfies the above-mentioned requirements for both oilless fixing property and blocking resistance, and stability of development and transfer, and the like. A new manufacturing method is required to achieve this. JP-A-5-127422 discloses a method in which an oil phase solution in which a toner component is dissolved is formed into particles in an aqueous phase containing a water-soluble resin. A method of forming particles in an aqueous phase containing a dispersant has been proposed. Also, JP-A-7-168395 or JP-A-7-27109
No. 9 discloses an inorganic dispersant having a particle size of 0.1.
Tricalcium phosphate and hydroxyapatite of 7-5 μm have been proposed. However, in these proposals, there is no description that a release agent such as wax is added as a toner composition, the amount of wax on the surface and the inside is controlled within a certain range, and both the anti-blocking property and the oilless fixing property are achieved at a high level. There is no. Further, actually, Japanese Patent Application Laid-Open No.
When toner is formed by adding a wax using the method described in Japanese Patent No. 68395 or JP-A-7-271099, although particles of polyester can be actually produced, the particle size distribution becomes extremely wide and is not suitable for toner. It was found that the toner amount of the ultrafine powder having a particle size of ２2 μm or less was increased, and it was difficult to remove the toner even by mechanical classification. In addition, some colorants used as color toners increase the amount of fine particles of the toner, which is a problem.

Furthermore, one of the important functions required of a copying machine or a printer in recent years is a demand to output a clear image from a color image on a recording material other than paper. The requirement of forming a fixed image thereon and creating an explanatory transparency (transparent original) using OHP is important in the field of color. However, some color toners obtained by the pulverization method or the polymerization method to which the wax is added are insufficient in color due to insufficient dispersion of the wax.
In some HP images, only extremely insufficient transparent images were obtained. In particular, when a low-molecular-weight polyester is used as a binder resin and a low-molecular-weight wax is used as a release agent, the pulverization method toner does not have a sufficient share at the time of melt-kneading, so that the above-described problem becomes remarkable. Regarding the problem concerning the production of a toner having both oil-less fixability and high transferability, that is, evenly dispersing a wax as a release agent in a toner resin, particularly preferably a polyester resin, is still suitable. At present, no solution has been obtained.

[0012]

The first object of the present invention is to provide an advantage in designing a small and inexpensive copier or printer without causing the above-mentioned problems or disadvantages. It is an object of the present invention to provide a novel toner which does not need to supply oil to a fixing system, a developer containing the same, and a simple method for producing the toner. The second problem to be solved by the present invention is to provide a new level of compatibility between oilless fixing properties, powder properties of a toner using wax, filming properties, and high transfer properties required for color images at a high level. It is an object of the present invention to provide a toner, a developer and a method for producing a toner. A third problem to be solved by the present invention is to provide an image forming method using a new toner having high color image quality and good OHP transmission image.

[0013]

As a result of intensive studies on these problems, we have found that the following problems can be solved without the above-mentioned problems or disadvantages by using the following toner and toner manufacturing method. The discovery has been completed.

That is, the toner for an electrostatic latent image developer according to the present invention is a toner for an electrostatic latent image developer comprising a binder resin and a colorant, wherein the toner contains 0.1 to 40% by weight of wax.
1 to 1 wax contained and exposed on the toner surface
0% by weight, and the number average dispersion diameter of the wax is 0.1 to
2 μm, preferably characterized in that the wax particles have a flaky shape.

The electrostatic latent image developer of the present invention is a two-component developer comprising a carrier and a toner, wherein the toner contains 0.1 to 40% by weight of a wax, and Is 1 to 10% by weight, and the wax has a number average dispersion diameter of 0.1 to 2 μm.

Further, the method for producing a toner for an electrostatic latent image developer according to the present invention is a method for producing a toner for an electrostatic latent image developer containing at least a resin, a colorant and a wax. Dissolving or dispersing each raw material of wax in an organic solvent to form an oil phase component, and granulating the oil phase component in an aqueous solvent, the toner formed by the granulation step It is characterized in that the wax contained therein has a number average dispersion diameter of 0.1 to 2 μm. Further, the production of the toner can also be performed by applying a suspension polymerization method.

The toner of the present invention comprises a wax having a low melting point,
Since the toner is present on the inside and the surface of the toner in a preferable range, the toner has good toner performance with good peeling from the fixing roll and good heat blocking property. For this reason, it is possible to design a small and inexpensive color copying machine or printer that does not need to supply oil to the fixing system. Further, according to the method for producing a toner of the present invention, a low-melting-point wax, which has been difficult to use in a conventional kneading and pulverizing method, can be suitably used. The polymerization method can be dispersed in a polyester resin, which has been difficult to use as a binder resin, and the shape of the toner can be controlled, so that a toner having good powder characteristics and high transfer efficiency can be obtained. Design becomes possible. According to the toner production method of the present invention, since the finely divided wax is used, the dispersion unit of the wax in the toner can be finely dispersed, so that a color image quality is high, and in particular, a toner having a good OHP transmission image can be provided. .

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

First, a method for producing a toner for an electrostatic latent image developer (hereinafter, simply referred to as toner) of the present invention and a structure of the obtained toner will be described. In the toner structure of the present invention, in order to generate oil droplets of the toner composition in an aqueous phase composed of an aqueous solvent, a component having a polar group and a non-polar component such as wax contained in the toner composition are hydrophilic. It is based on the effect of structuring the inside of the toner and the surface wax by the difference in hydrophobic affinity. As a result, the toner of the present invention has a wax content of 0.1% by weight to 40% by weight.
It was found that the ratio of the wax exposed on the toner surface was controlled in the range of 1% by weight to 10% by weight.

The amount of the wax added to the toner particles depends on the average dispersion diameter of the finely divided wax, and is usually from 0.1% by weight to 40% by weight.
More preferably, it is in the range of 15 to 15% by weight. If the amount is less than 0.1% by weight, the desired roll release property cannot be obtained,
When it exceeds, the blocking resistance of the toner decreases,
This is because the transparency of the image after fixing is reduced. When the amount of wax on the surface of the toner is less than 1% by weight, sufficient offset resistance cannot be obtained. Neither of them is preferable, because the mining becomes remarkable.

In the present invention, the proportion of the wax exposed on the toner surface can be measured by ESCA surface elemental analysis. Elemental analysis of the surface by ESCA means that the elements on the toner surface are measured to determine the elemental composition ratio of the surface, then the molecular formula of each compound contained in the toner is determined, and the surface composition is determined from the elemental composition ratio of the surface measured by ESCA. This is a method for calculating the content of each compound present in the compound. The measurement conditions for the ESCA analysis used in the present invention are described below.

Measuring device: X-ray photoelectron spectrometer Esca
-Lab-220i, manufactured by VG Measurement conditions: X-ray source Mg (300 W), Passe
energy = 30 eV, sampling = 0.1 eV
Step, dwell time = 100 ms The method of quantitative calculation is described. First, the carbon = C1s spectrum of the toner was separated into respective components using curve fitting by the least square method. As the components used for the fitting, C1s spectra obtained by independently measuring each material constituting the toner were used. At this time, a fitting program was used for the fitting process. The element ratio (Atomic Concentrat) determined above
ion), the amount of each compound present on the surface was calculated.
The calculation method is based on the above-mentioned AtomicConcentrat
The composition ratio of each constituent compound was determined using ion. That is, the element ratio of the constituent compounds was separately determined, then the number ratio of the constituent compounds was determined from the element ratio present on the toner surface, and the weight ratio was calculated by multiplying the molecular weight of each compound by the number ratio. Thus, the proportion of the wax present on the surface was determined. The surface in the present invention is defined to be 0.1 μm deep from the outermost surface. The above-described surface existence ratio by ESCA can be measured from a depth of about several nm to about 0.5 μm by a technique such as etching.

The proportion of the surface wax present in the ordinary kneaded and pulverized toner slightly changes depending on the absolute amount of the wax contained.
Range.

The wax used in the toner of the present invention has a melting point of 110 ° C. or less or a latent heat of melting of 230 mJ.
/ Mg or less low melting point wax more effectively acts as a release agent between the fixing roller and the toner interface, thereby preventing high temperature offset without applying a release material such as oil to the fixing roller. Turned out to be possible.

The melting point is 110 ° C. or more or the latent heat of melting is 2
If it is 30 mJ / mg or more, the effect of the releasability is not sufficient. When the melting point is 30 ° C. or lower, the blocking resistance and the storage stability of the toner may be insufficient, which is not preferable. In addition, the melting point of the wax in the present invention was defined as a maximum endothermic peak by a differential scanning calorimeter (DSC).

The following materials can be used as the wax component functioning as a release agent that can be used in the present invention. That is, as specific examples, as waxes and waxes, carnauba wax, vegetable wax such as cotton wax, wood wax, rice wax, beeswax, animal wax such as lanolin, ozokerite, mineral wax such as celsin, And petroleum waxes such as paraffin, microcrystalline, petrolatum and the like. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones and ethers can be given. Further, 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride, fatty acid amides such as chlorinated hydrocarbons, and poly-n-stearyl methacrylate, which is a low molecular weight crystalline polymer resin,
Homopolymer or copolymer of polyacrylate such as poly n-lauryl methacrylate (eg, copolymer of n-stearyl acrylate-ethyl methacrylate)
For example, crystalline polymers having a long alkyl group in the side chain can be used. Of these, more preferred are petroleum waxes such as paraffin wax and microcrystalline wax or synthetic waxes.

[0027] When a transparency film is used as a recording material (recording medium), the problem that the transparency of an image after fixing is slightly reduced depends on the dispersion unit of wax contained in the toner. It was confirmed that. That is, if the dispersion unit of the wax in the toner is dispersed so as to have a particle size that hardly affects the transmittance, the problem of the transmittance is eliminated regardless of the degree of crystallinity of the wax. Specifically, the average particle size (here, number average particle size) of the wax dispersed in the toner is 2 μm to 0.1 μm.
m, more preferably in the range of 1 μm to 0.1 μm. For this purpose, the wax used when preparing the toner is
It is necessary to use wax which has been previously finely divided to an average particle size of 2 μm or less, more preferably 1 μm or less. If the average particle diameter of the wax dispersed in the toner exceeds 2 μm, the transparency of an image after fixing when using a transparency film is reduced. If the average particle size of the wax is less than 0.1 μm, the releasing performance becomes insufficient.

The average particle size of the wax can be measured as follows. The toner is solidified with a binder resin such as epoxy, sliced with a microtome to a thickness of about 1000 angstroms, and observed with a transmission light microscope, whereby wax particles having phase separation can be seen. In the present invention, in order to minimize the error due to the section of the grain, 10
The points were measured, and the average of the five large points was taken as the average particle size.

To make the wax finer, for example, 1995
Engineering Research Report published by the Society of Polymer Science, Japan March 1
Fine particles may be formed by any conventionally known method using an emulsification / dispersion device or the like described in “Emulsification / Dispersion Technology and Control of Particle Size of Polymer Fine Particles, Chapter 3”. In addition, using an appropriate solvent that is compatible with the solvent used in preparing the toner and does not dissolve the wax at room temperature, add the wax to the above solvent, dissolve by heating, and gradually cool to room temperature to precipitate fine particles of wax. A method in which the wax is heated and evaporated in an inert gas such as helium to produce particles in the gas phase, and the particles are attached and collected on a cooled film or the like, and then dispersed in a solvent. (Gas phase evaporation method)
Can be applied. Further, it is more effective to combine these methods with the mechanical pulverization method using the emulsifying / dispersing device or the like. That is, in order to achieve a desired fine particle size using only the mechanical pulverization method, a high shear force is applied, but when the temperature is increased by the high shear force, the low melting point wax is undesirably affected. This is because there is a fear.

In the present invention, the fine wax particles preferably have a flaky shape. Here, the term “flaky” means that the maximum length in the vertical direction is at least twice the thickness and the maximum length in the horizontal direction is at least 1.5 times the thickness of the wax particles. How to determine the vertical, horizontal, and thickness directions of the wax particles in the present invention will be described with reference to the wax particle model diagram of FIG. The longitudinal direction of the wax particles is the longest diagonal direction of the particles, and is indicated by the line A in FIG. In addition, the direction in which the maximum width of the projection viewed from the direction perpendicular to the longest diagonal line (A) is the shortest is defined as the thickness direction and is indicated by line C in FIG. In FIG. 1, the vertical direction with respect to the vertical direction and the thickness direction is defined as
This is indicated by the line. The maximum length in the vertical direction is at least twice the thickness and the maximum length in the horizontal direction is at least 1.5 times the thickness with respect to the thickness defined in this manner. Preferably, it is present in a proportion of at least 75% of the total number. In the case of such flaky wax particles, the thickness is 0.5 μm or less. 0.2μ
m or less.

By making the wax particles flaky in this way, the melting of the wax is accelerated, and the wax distributed inside the toner can also be melted quickly as compared with the spherical wax particles. Since the shape is long in the vertical direction, the amount of wax existing near the toner surface increases, and the offset property of the wax tends to be efficiently exhibited.

Also in the case of such flaky wax particles, the particles are preferably fine. The number of flaky wax particles having a maximum length of 5 μm or more is 10% or less of the whole, and the maximum length in the vertical direction is It is desirable that the number average is 1 μm or less. As the shape of the wax particles increases,
The light transmittance is reduced due to the scattering of light, and problems such as deterioration of the light transmittance of the OHP and deterioration of the color developability are likely to occur.

The wax particles are dispersed together with a resin and a colorant in an organic solvent, so that they are used after being dispersed in a solvent before preparing an oil phase component. The wax dispersion is applied to the mixture of wax and solvent by applying pressure to a high pressure state, and then spouted out of a minute gap such as a nozzle. It is desirable to prepare by making.

As a means for preparing the wax dispersion, a device for ejecting the mixture and a fine opening (nozzle) as shown in FIG. And the like. In the wax fine dispersion apparatus 40 shown in FIG. 2, a mixed solution of wax and a solvent is injected into a cylinder 42, and the inside of the cylinder 42 is pressurized in the direction of arrow A in the figure. If the internal pressure exceeds the pressure applied to B, a gap is formed between the valve 44 and the valve 44, and the mixed liquid ejected from the gap collides with the wall surface 46 at a high speed, and the wax is miniaturized. Such devices include, for example, A
A Gorin homogenizer manufactured by PV Co., Ltd., and the like. The wax fine dispersion device 48 shown in FIG. 3 is provided with a container 52 having pores 50. After a mixed solution of wax and a solvent is injected into the container 52, pressure is applied. When the pressure is low, the liquid does not pass through the fine holes, but when sufficiently pressurized, the mixed liquid spouts out of the fine holes and collides with the opposing wall surface 54 at a high speed, thereby making the wax fine.

[0035] Here, higher the pressure crushing force becomes higher, the temperature rise becomes vigorous, to produce a possibility to cause agglomeration of the wax, the pressure is preferably 50~1000kg / cm ^2, further 150~700kg / cm ² Is preferred.

In preparing the wax dispersion, it is desirable that the wax is dissolved or melted in a solvent by heating. Further, if necessary, the high-pressure ejection process as described above may be repeatedly performed, or the wax particles may be roughly dispersed in advance by a known wax dispersion method.

The binder resin of the toner for an electrostatic latent image developer according to the present invention is not particularly limited, and a resin generally used as a resin for a toner can be used. Specifically, polyester resin, styrene resin, acrylic resin, styrene / acrylic resin, silicone resin, epoxy resin, diene-based resin, phenolic resin, ethylene / vinyl acetate resin, etc. From the viewpoint of smoothness of the obtained image, a polyester resin is more preferable.

The following can be mentioned as the polymerized monomer of the polyester resin. Examples of the alcohol component include polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3) -2,2-bis (4-hydroxyphenyl) propane, Oxyethylene (2,0) -2,
2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2,0) -polyoxyethylene (2,
Diols such as 0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2,0) -polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, isopentyl glycol, dipropylene glycol, isopentyl glycol, hydrogenated bisphenol A, 1,3-butanediol, 1,4-butanediol , Neopentyl glycol, xylylene glycol,
1,4-cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, bis- (β-hydroxyethyl) terephthalate, tris- (β-hydroxyethyl) isocyanurate, 2,2,4-trimethylol Pentane
1,3-diol and the like. Further, a hydroxycarboxylic acid component can be further added to the alcohol component in order to impart properties of the polyester resin.
For example, p-oxybenzoic acid, vanillic acid, dimethylolpropionic acid, malic acid, tartaric acid, 5-hydroxyisophthalic acid and the like.

Specific examples of the acid component include malonic acid, succinic acid, glutaric acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, dimethyl isophthalate, dimethyl terephthalate, monomethyl terephthalate, tetrahydroterephthalic acid , Methyltetrahydrophthalic acid, hexahydrophthalic acid, dimethyltetrahydrophthalic acid, endomethylene hexahydrophthalic acid, naphthalenetetracarbic acid, diphenolic acid, trimellitic acid, pyromellitic acid, trimesic acid, cyclopentanedicarboxylic acid, 3 , 3 ', 4,4'-benzophenonetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 2,2-bis- (4-carboxyphenyl) propane, trimellitic anhydride and 4,4 -From diaminophenylmethane Ring obtained from trimerization product of diimide carboxylic acid, tris- (β-carboxyethyl) isocyanurate, polyimide carboxylic acid containing isocyanurate ring, tolylene diisocyanate, xylylene diisocyanate or isophorone diisocyanate and trimellitic anhydride Containing polyimide carboxylic acid, and one or more of these are used. Of these, the use of a crosslinking component such as a trivalent or higher polyhydric carboxylic acid or polyhydric alcohol may be preferable in terms of stability such as fixing strength and offset resistance.

The polyester resin obtained from these raw materials is produced by a usual method. Glass transition temperature is 40
It is convenient to set the temperature between 0C and 80C, more preferably between 50C and 70C. Two or more of the above polyester resins may be combined with the resin of the present invention, and other resins may be combined as long as the effects of the present invention are not impaired. Other resins include styrene resin, acrylic resin, styrene / acrylic resin, silicone resin, epoxy resin, diene resin, phenol resin, terpene resin, coumarin resin, amide resin, amide imide resin, butyral resin, urethane resin, ethylene There are vinyl acetate resins and the like. In the present invention, it is preferable to add a polyester resin as a main component and other resins in an amount of 0 to 30 parts by weight in the toner.

In the present invention, as the colorant to be dispersed in the above-mentioned thermoplastic resin, known organic or inorganic pigments and dyes, and oil-soluble dyes can be used.
For example, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 1
22, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 1
2, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 3, Lamp Black (CIN
o. 77266), Rose Bengal (CI No. 4)
5432), carbon black, nigrosine dye (C.I.
I. No. 50415B), metal complex dyes, derivatives of metal complex dyes, and mixtures thereof. Further, various metal oxides such as silica, aluminum oxide, magnetite and various ferrites, cupric oxide, nickel oxide, zinc oxide, zirconium oxide, titanium oxide, and magnesium oxide, and a suitable mixture thereof, and the like. Can be

It is necessary that these colorants are contained in a sufficient ratio to form a visible image having a sufficient density, and it depends on the toner particle size and the development amount.
A ratio of about 1 to 100 parts by weight with respect to 00 parts by weight is appropriate.

In the present invention, a charge control agent may be added to the toner if necessary. Usable charge control agents include metal salts of benzoic acid, metal salts of salicylic acid, metal salts of alkylsalicylic acid, metal salts of catechol, metal-containing bisazo dyes, and tetraphenylborate derivatives used in powder toners , Quaternary ammonium salts and alkylpyridinium salts, as well as those suitably combined.

The amount of the charge control agent added to the toner is generally from 0.1% by weight to 10% by weight,
It is in the range of 0.5 to 8% by weight. When the amount is less than 0.1% by weight, the charge control effect is insufficient, and when the amount exceeds 10% by weight, the toner resistance is excessively reduced, which makes it difficult to use.

Further, a metal soap, an inorganic or organic metal salt can be used in combination with the charge control agent. Such metal soaps include aluminum tristearate, aluminum distearate, barium, calcium, lead and zinc stearate, or cobalt,
Manganese, lead and zinc linolenate, aluminum,
Calcium, cobalt octanoate, calcium and cobalt oleate, zinc palmitate, calcium, cobalt, manganese, lead and zinc naphthenates,
Resinates of calcium, cobalt, manganese lead and zinc can be used. As the inorganic and organic metal salts, for example, the cationic component in the metal salt is selected from the group consisting of metals of Groups Ia, IIa, and IIIa of the periodic table, and an anion of the acid. The sexual component is a salt selected from the group consisting of halogen, carbonate, acetate, sulfate, borate, nitrate, and phosphate. These charge control or cleaning aids generally range from 0.1% to 10% by weight, more preferably from 0.1% to 5% by weight, based on the toner.
If it is less than 0.1% by weight, the desired effect is insufficient,
On the other hand, if the content exceeds 10% by weight, the fluidity of the toner powder is reduced, which is not preferable.

Next, a method for producing a toner according to the present invention will be described. In the present invention, a binder resin of a toner represented by a polyester resin, a colorant, and other additives used as necessary are dissolved or dispersed in a solvent in which the resin is soluble, and an oil phase is formed. . The solvent that can be used depends on the components of the binder resin, but generally, toluene,
Hydrocarbons such as xylene and hexane; halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane;
Alcohols or ethers such as ethanol, butanol, benzyl alcohol, ether and tetrahydrofuran, esters such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate, acetone and methyl ethyl ketone;
Ketones such as diisobutyl ketone, cyclohexanone, and methylcyclohexane are exemplified. These solvents are
It is necessary to mainly dissolve the polyester resin, but the coloring agent and other additives may or may not be dissolved. The weight ratio of the toner component to the solvent used in the oil phase is preferably from 10/90 to 80/30 from the viewpoint of easy granulation or the final toner yield.

Next, the obtained oil phase is granulated in an aqueous phase (a water-soluble solvent) so as to have a predetermined particle size. The main medium of the aqueous phase is water. If necessary, the following inorganic dispersion stabilizers and / or organic dispersion stabilizers forming hydrophilic colloids may be added. Examples of the inorganic dispersion stabilizer include calcium carbonate, magnesium carbonate, barium carbonate, tricalcium phosphate, hydroxyapatite, diatomaceous earth silicate, and clay. The particle size of these inorganic dispersion stabilizers is preferably 0.1 μm or less. These are ball mills,
It is desirable to use it after pulverizing to a desired particle size by a wet disperser such as a sand mill or an attritor. When the particle size of these inorganic dispersion stabilizers exceeds 2 μm, the particle size distribution of the granulated toner becomes wide and cannot be used as a toner.

Specific examples of the organic dispersion stabilizer which can be used in combination with these inorganic dispersion stabilizers include gelatin and gelatin derivatives (eg, acetylated gelatin, phthalated gelatin,
Succinated gelatin, etc.), proteins such as albumin, casein, collodion, acacia, agar, alginic acid,
Cellulose derivatives (for example, alkyl esters of carboxymethylcellulose, hydroxymethylcellulose, carboxymethylcellulose, etc .; synthetic polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylate, polymethacrylate, polymaleate, polystyrene sulfonate), etc. These organic dispersion stabilizers are preferably those that form a hydrophilic colloid, and may be used alone or in combination of two or more. It is preferably used in the range of 0.001 part by weight or more and 5 parts by weight or less.

Further, a dispersion stabilizing aid may be used in combination with the aqueous phase. Various surfactants are suitable for the dispersion stabilizing aid, and examples of the surfactant include ionic and nonionic surfactants. Specifically, as an anionic surfactant, alkyl benzene sulfonate,
Alkyl phenyl sulfonate, alkyl naphthalene sulfonate, higher fatty acid salt, higher fatty acid ester sulfate, higher fatty acid ester sulfonic acid, and the like can be used. As the cationic activator, primary to tertiary amine salts, quaternary ammonium salts and the like can be used. Non-ionic activators include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester And fatty acid alkylolamides. These dispersion stabilizing aids may be used alone or in combination of two or more. The dispersion stabilizing aid is preferably used in a range of 0.001 part by weight or more and 5 parts by weight or less based on the main medium of the aqueous phase.

The mixing of the oil phase and the aqueous phase varies depending on the final particle size of the toner and the production equipment, but is preferably in the range of usually 10/90 to 90/10 by weight.

The granulation of the oil phase in the aqueous phase is preferably performed under high-speed shearing. In particular, when the particle size of the toner is desired to be in the range of 5 to 9 μm, the selection of the disperser to be used is considered,
It is necessary to select one with a high-speed shearing mechanism. Among them, a high-speed blade rotation type or forced interval passage type emulsifier such as various homomixers, homogenizers, and colloid mills are preferably used.

The solvent is removed at the same time as the step of granulating the toner or after the step of granulating. The removal of the solvent may be performed at normal temperature or may be performed under reduced pressure. In order to perform the reaction at room temperature, it is necessary to apply a temperature lower than the boiling point of the solvent and in consideration of the Tg of the resin. If the Tg of the resin is greatly exceeded, undesirable coalescence of the toner may occur. Usually, it is convenient to stir at about 40 ° C. for 3 to 24 hours. It is convenient to reduce the pressure at 20 to 150 mmHg.

After the solvent was removed, hydrochloric acid,
It is preferable to wash with an acid such as nitric acid, formic acid, and acetic acid that makes the inorganic dispersion stabilizer water-soluble. When the inorganic dispersion stabilizer and the organic dispersion stabilizer described above remain on the toner surface, the humidity dependency of the chargeability of the toner is deteriorated due to the hygroscopic property of the remaining deposits. It is necessary to remove inorganic and organic dispersion stabilizers. It is necessary to remove this dispersion stabilizer as much as possible to minimize the influence on the chargeability and powder flowability of the toner.

The toner washed with the above acid may be washed again with an alkaline water such as sodium hydroxide if necessary. As a result, a part of the ionic substance on the toner surface which has been insolubilized by being placed in an acidic atmosphere is again solubilized and removed, which is favorable for the charging property and the powder fluidity.

Further, such washing with an acid or alkaline water has an effect of washing and removing wax which has been released and adhered to the toner surface. By performing both the acid washing step and the alkali washing step, the neutralization is performed after the removal of the wax and the like. When performing the acid cleaning step and the alkali cleaning step, either step may be performed first. In these cleaning steps after toner formation, in addition to controlling conditions such as pH at the time of cleaning, the number of times of cleaning, and temperature at the time of cleaning, the cleaning is effectively performed by using a stirrer or an ultrasonic dispersion device. Convenient.
Thereafter, if necessary, steps such as filtration, decantation, and centrifugation are performed, and after drying, the toner particles of the present invention are obtained.

A known external additive may be added to the toner of the present invention in order to control fluidity and developability. As the external additive, various inorganic oxide fine particles such as silica, alumina, titania, and cerium oxide, and if necessary, hydrophobic fine particles, a vinyl polymer, and zinc stearate can be used. The external addition amount is preferably in the range of 0.05 to 5 parts by weight with respect to the toner before addition.

The shape of the toner of the present invention can be changed from a spherical shape to an irregular shape or by controlling the difference in toner production conditions, in particular, the prescription of the toner material and the process conditions for evaporating the solvent from the toner after granulation. Small irregularities, wrinkles,
It is also possible to obtain a toner shape having holes and projections.
Specifically, it is preferable that the shape factor MLS2 is controlled in the range of 100 to 140 from the viewpoint of the characteristics of the obtained developer.

Here, the MLS2 means, for example, using FE-SEM (S = 800) manufactured by Hitachi, Ltd., randomly sampling 100 toner images magnified 500 times,
The image information is introduced into, for example, an image analyzer (Luzex-II) manufactured by Nireco via an interface, analyzed, and a value (shape-based numerical value ML) obtained by the following equation is calculated.
S2).

MLS2 = (absolute maximum length of toner particles) 2
/ (Projected area of toner particles) × π × １ ／ × 100 The toner particles of the present invention can be controlled in the range of 100 to 140 by MLS2 by being manufactured by the above-described manufacturing method. The shape of the toner produced by the ordinary kneading and pulverizing method is irregular, and when MLS2 is measured, it is 140 to
It is about 160. In MLS2, 100 indicates a true spherical shape.

The toner obtained by the production method of the present invention can be used without limitation in the known dry electrostatic developing method. For example, a two-component developing method such as a cascade method, a magnetic brush method, or a microtoning method, a one-component developing method such as a conductive one-component developing method, an insulating one-component developing method, and a non-magnetic one-component developing method can be mentioned. However, it is also possible to design a unique process that effectively uses the low toner adhesion caused by the spherical toner shape described above. In other words, when using a full-color copying machine that can develop and transfer multiple toner images, the amount of toner on the photoreceptor increases compared to conventional monochrome toner, and transfer efficiency is improved by using only conventional amorphous toner. It is difficult to do. For this reason, in the color image formation, it is difficult to transfer the four color toners uniformly, and when using the intermediate transfer, it is easy to cause problems in color unevenness and color balance, and a high quality full color image can be stably formed. It was difficult to output. As a result of examining the correlation between the transfer efficiency problem and the toner shape, the ML
It became clear that a decrease in toner transfer efficiency was observed around S2 exceeding 140. As described above, the toner for an electrostatic latent image developer of the present invention has an MLS2 of 100 to 100.
The shape can be controlled in the range of 140, and the MLS2 suitable for increasing the transfer efficiency can be about 100 to 120 by adjusting the toner production conditions. Therefore, by using the toner of the present invention, it is possible to design a small and simple process utilizing the high transfer efficiency characteristics of the toner and employing no cleaning member.

The toner of the present invention can be combined with a carrier to form an electrostatic image developer suitable as a two-component developer in the same manner as a normal toner.

When the carrier is used as a two-component developer, the carrier may be iron powder, glass beads, ferrite powder, nickel powder, magnetite powder, a resin coated on the surface thereof, or a resin and a charge controlling agent. And the like are kneaded with a magnetic material, pulverized and classified, and a resin-dispersed carrier obtained can be used. Here, as the carrier used in combination with the toner,
It is preferable that the inorganic particles have a resin coating layer in which the surface of the inorganic particles is coated with a resin.

Next, the image forming method of the present invention will be described. An image forming method according to the present invention includes the steps of forming a latent image on an image carrier, developing the latent image using a developer, and transferring the formed toner image onto a transfer body. A toner containing a binder resin, a colorant, and a wax as the developer, wherein the toner contains 0.1 to 40% by weight of the wax, and the wax exposed on the toner surface is 1 to 4% by weight. It is characterized by using an electrostatic latent image developer containing 10% by weight and a toner having a wax having a number average dispersion diameter of 0.1 to 2 μm.

Here, the process designed using the toner of the present invention will be described with reference to specific examples. However, the process is not limited to this as long as the toner of the present invention is used.

FIG. 4 is a schematic diagram showing the configuration of an image forming apparatus 10 which can be suitably used in the image forming method of the present invention.

The photosensitive member 12 is made of a-Se, OPC, a-S
i, composed of a photosensitive drum or belt having a photoconductive insulating layer such as ZnO. Among them, OPC and a-Si photoconductor are preferably used. In this specific example, in the charging step in the step of forming a latent image, a corona charger 14 is used, and a non-contact type with the photoconductor is used. As another method, a contact type using a roller or a magnetic brush can also be used. After charging, the latent image that has passed through the exposure device 15 is transported to a developing device. This embodiment is a full-color machine, and cyan, magenta, yellow, and black developers are introduced into the developing units 16c, 16m, 16y, and 16b, respectively. The developing method may be a magnetic brush developing method or a non-magnetic one-component developing method. The intermediate transfer member 18 has a pipe-shaped conductive core 18b provided with an elastic layer 18a whose electric resistance value is controlled. Further, if necessary, a detachable cleaning means 20 as shown in the figure is provided. The toner image on the intermediate transfer body 18 is applied with a bias having a polarity opposite to the frictional charge of the toner by the transfer charger 22 and is transferred onto the surface of the transfer material 24. The transfer material 24 on which the toner image is formed finally passes between a heating roll (heat fixing roll) 26 having a built-in heating element such as a halogen heater and an elastic pressing roll 28 pressed with a pressing force. Thus, the toner image is fixed on the transfer material 22.

Even when such a simple device is used,
By using the toner of the present invention that can achieve both the oilless fixing property and the transfer property, a high quality image can be formed.

[0068]

The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited by the following Examples and Comparative Examples. In Examples and Comparative Examples, “parts” means “parts by weight”. [Developer Evaluation Method] (1) Evaluation of Toner Developability and Fixability As an image output evaluation device, a device modified from A color 635 (manufactured by Fuji Xerox Co., Ltd.) was used. FIG. 4 shows an outline of the image output evaluation apparatus. In particular, for evaluation of oil-less fixing property, image evaluation was performed without supplying oil to the heat fixing roll.

The specific experimental conditions are as follows. Photoconductor OPC (φ84) ROS LED (400 dpi) Process speed 160 mm / s Latent image potential Background part = -550 V, image part = -150 V Developing roll (common to first to fourth developing units) Magnet fixing, sleeve rotation, magnet magnetic flux Density = 500G (on the sleeve), sleeve diameter = φ25, sleeve rotation speed = 300 mm / s, interval between the photoconductor and the developing roll (common to the first to fourth developing units) 0.5 mm, developer layer layer thickness regulating member, and developing roll (Common to the first to fourth developing devices) 0.5 mm Developing bias (common to the first to fourth developing devices) DC component = −500 V, AC component = 1.5 kVP-P
(8 kHz) Transfer conditions Corotron transfer (wire diameter = 85 μm) Fixing conditions No fluoresol, oil supply Evaluation environment: normal temperature and normal humidity (23 ° C., 50% RH) and high temperature and high humidity (23 ° C., 50% RH) (Image quality evaluation method ) Image density: Color reflection densitometer (Color refl)
action-densitometer X-RIT
E 404A) Color tone reproducibility: An image was formed on an OHP sheet, and the transmittance of each color was measured at the following wavelengths. As a device for measuring the transmittance, a spectrophotometer U-3210 (manufactured by Hitachi, Ltd.) was used. Cyan 480 nm Magenta 680 nm Yellow 580 nm Fixed image strength evaluation: Image is formed on plain paper, and judged based on the following criteria. did. Good --- --- The image fixed at a roll temperature of 180 ° C is squeezed and no toner is peeled. Inferior --- --- The image is hardened and toner is peeled (2).
Evaluation of Transfer Efficiency To measure the transfer efficiency 1 from the photoreceptor to the intermediate transfer body, a toner image on the photoreceptor is collected with a transparent adhesive tape, and the image is measured with a color reflection densitometer. Next, a toner image was prepared again, the toner image was transferred to the intermediate transfer member, and similarly collected with an adhesive tape, and the image density was measured. The transfer efficiency is calculated as follows.

Transfer efficiency 1 = (density of toner image collected from intermediate transfer member) / (density of toner image collected from photosensitive member) Similarly, transfer efficiency from the intermediate transfer member to the transfer material is calculated as follows.

Transfer efficiency 2 = (density of toner image collected from transfer material) / (density of toner image collected from intermediate transfer member) The final transfer efficiency is calculated as follows.

Final Transfer Efficiency = Transfer Efficiency 1 × Transfer Efficiency 2 (3) Evaluation of Thermal Blocking of Toner 5 g of the toner was left in a chamber at 45 ° C. and 50% RH for 17 hours. After reaching room temperature, 2 g of toner was
It was put into a 5 μm mesh and vibrated under certain conditions.
The weight of the toner remaining on the mesh was measured, and the weight ratio was calculated. This value was taken as the toner heat blocking index. (Example 1) (A) Preparation of pigment dispersion A pigment dispersion was prepared by the following procedure.

1. 1. Polyester resin R-1 (details are described in Table 1 below): 50 parts (Tg; 63 ° C., softening point; 102 ° C., weight average molecular weight; 9000) 2. Copper phthalocyanine pigment: 50 parts (CI Pigment Blue 15: 3, Cyanine Blue 4933M; manufactured by Dainichi Seika) 100 parts of ethyl acetate

[0074]

[Table 1]

Glass beads were added to the dispersion of the above-mentioned material composition, and the dispersion was mounted on a sand mill disperser. While cooling around the dispersion container, the mixture was dispersed in a high-speed stirring mode for 3 hours to obtain a pigment concentration of 10%.
A pigment dispersion having a concentration of% by weight was prepared. (B) Preparation of Micronized Wax A dispersion of micronized wax was prepared by the following procedure.

1. 1. Paraffin wax: 15 parts (melting point: 85 ° C., latent heat of fusion: 193 mJ / mg) Toluene 85 parts The above material was equipped with stirring blades and a heat medium was circulated around the vessel.
Into a dispersing machine with the function of Stir at 83 rpm
Gradually increase the temperature while stirring, and finally to 100 ° C
Stirring was continued for 3 hours. Next every minute while stirring
A wax that has been cooled to room temperature at a rate of about 2 ° C.
Was precipitated. Laser diffraction / scattering particle size distribution analyzer LA
-700 (Horiba, Ltd.)
It was about 1.02 μm when measured. This wax dispersion
The liquid is subjected to a high-pressure emulsifier (APV GAULIN HOMOGE)
NIZER 15MR type), pressure 500kg / c
m ^TwoAgain to perform dispersion. Measure the wax particle size in the same way
As a result, it was 0.81 μm. The micronized wafer
The wax dispersion has a wax concentration of 15% by weight.
And diluted with ethyl acetate. (C) Preparation of Oil Phase The toner oil phase was prepared by the following procedure.

1. 1. Polyester resin R-1 (described in Table 1): 85 parts (Tg; 63 ° C., softening point; 102 ° C., weight average molecular weight; 9000) 2. Pigment dispersion liquid: (Pigment concentration: 10% by weight) 50 parts 3. Particulate wax dispersion: (15% by weight of wax) 33 parts Ethyl acetate 32 parts The oil phase of the above material composition was adjusted after confirming that the polyester resin was sufficiently dissolved. The oil phase was charged into a homomixer (Ace Homogenizer, manufactured by Nippon Seiki Co., Ltd.), and stirred at 15,000 rpm for 2 minutes to prepare a uniform oil phase. (D) Preparation of aqueous phase The aqueous phase was prepared by the following procedure.

1. 1. Calcium carbonate: (average particle size 0.03 μm) 60 parts 40 parts of pure water The above-mentioned material was stirred with a ball mill for 4 days. The average particle size of calcium carbonate measured using the above-mentioned laser diffraction / scattering particle size distribution analyzer LA-700 (Horiba Seisakusho) was about 0.08 μm. Meanwhile, 1. 1. Carboxymethylcellulose (Selogen BSH; Daiichi Kogyo Seiyaku) 2 parts 98 parts of pure water was dissolved to obtain an aqueous phase. (E) Toner Production Method The following materials were prepared as a toner production method.

1. Oil phase (C): 60 parts 2. 2. Calcium carbonate aqueous solution (D): 10 parts Carboxymethylcellulose aqueous solution (D): 30 parts The above materials were charged into a colloid mill (manufactured by Nippon Seiki Co., Ltd.), and emulsified at a gap interval of 1.5 mm and 8000 revolutions per minute for 20 minutes. Next, the above emulsion was put into a rotary evaporator, and the solvent was removed under reduced pressure of 30 mmHg at room temperature for 3 hours. Thereafter, 12N hydrochloric acid was added until the pH reached 2, and calcium carbonate was removed from the toner surface. Thereafter, 10N sodium hydroxide was added until the pH reached 10, and stirring was continued for one hour while stirring with an agitator in an ultrasonic cleaning tank. The supernatant was further centrifuged and the supernatant was exchanged three times, washed and dried to take out the toner. The volume average particle size of the toner measured using a Coulter Counter TA-II (manufactured by Coulter) is 7.8 μm.
m, GSD (Geometric Standard)
Di-vision: the root of d84 / d16, which is the volume average particle size, is 1.22, and the shape factor MLS2 is 1.
07. Further, the wax content in the toner is set to M
Differential thermal analysis (DSC) was performed using a thermal analyzer DSC3110 manufactured by AC Company, and the content was 4.8% by weight as determined from the endothermic peak area of the wax.

Further, the coloring agent may be C.I. I. Pigment Yellow 17, C.I. I. Pigment Red 57 and carbon black (# 4000, manufactured by Mitsubishi Kasei), and a yellow toner, a magenta toner and a black toner were obtained in the same manner. The physical properties of each color toner are shown in Table 2 below.

[0081]

[Table 2]

(F) Preparation of Developer and Evaluation on Actual Machine To the toner prepared in (E), 0.5 parts by weight of silica (R972: manufactured by Nippon Aerosil Co., Ltd.) was added using a Henschel mixer. F300 as a carrier core for this toner
(Powder Tech) with 0.5% methyl methacrylate
A carrier coated with parts by weight and a kneader was prepared, and adjusted to 8% by toner weight concentration to prepare a developer. Each color developer had a charge amount of -15 to -20 [mu] C / g. The transfer efficiency of each color from the photoconductor 12 to the intermediate transfer member 18 is 98 to 99%,
Transfer efficiency to 98-99%, and 96-
It showed a high transfer efficiency of 8%. The obtained image was good with high resolution, and there was no offset to the transfer material.

Further, continuous copying of 30,000 sheets was performed, but the image after 30,000 sheets was good without any change from the initial state. The image was evaluated at high temperature and high humidity, but no image disorder was found. Table 3 below shows the image hot offset temperature, fixing strength, OHP transmittance, and toner heat storage index of each color toner.

[0084]

[Table 3]

(Examples 2 to 6) Polyester resin R-1 described in Example 1 was changed from polyester R-2 having a monomer type shown in Table 1 to R-6, and further changed to Table 6 A toner was prepared in the same manner as in Example 1 except that the pigments and waxes described were used. Table 4 shows a list of the results of the evaluation performed in the same manner as in Example 1. The wax content in the toner was 4.7, 4.9, 4.6, respectively.
4.7, 4.5% by weight. Example 7 (A) A pigment dispersion was prepared by the following procedure.

[0086] 1. 1. Styrene-n-butyl acrylate resin: 50 parts (copolymerization ratio 70:30, Tg; 65 ° C., weight average molecular weight; 200000) C. I. Pigment Blue 15: 3 (Dainichi Seika Co., Ltd.) 50 parts 3. Ethyl acetate 100 parts Glass beads were added to the dispersion of the above-mentioned material composition, and the mixture was attached to a sand mill disperser. While cooling around the dispersion container, the mixture was dispersed in a high-speed stirring mode for 3 hours to prepare a pigment dispersion having a pigment concentration of 10% by weight. (B) A dispersion of micronized wax was prepared by the following procedure.

1. 1. Paraffin wax: 15 parts (melting point: 85 ° C., latent heat of fusion: 193 mJ / mg) Toluene 85 parts The above-mentioned material was charged into a dispersing machine having a function of circulating a heating medium around a vessel equipped with a stirring blade. The temperature was gradually increased while stirring at 83 revolutions per minute, and finally the mixture was stirred for 3 hours while maintaining the temperature at 100 ° C. Next, the mixture was cooled to room temperature at a rate of about 2 ° C. per minute while stirring was continued to precipitate wax in the form of fine particles. Laser diffraction / scattering particle size distribution analyzer LA
The average particle size of the wax measured using -700 (Horiba Seisakusho) was about 0.85 μm. The prepared dispersion liquid of the finely divided wax has a weight concentration of the wax of 15% by weight.
It was diluted with ethyl acetate to a concentration. (C) The toner oil phase was adjusted according to the following procedure.

1. 1. Styrene-n-butyl acrylate resin: 85 parts (copolymerization ratio 70:30, Tg; 65 ° C., weight average molecular weight; 200000) 2. Pigment dispersion liquid: (Pigment concentration: 10% by weight) 50 parts 3. Particulate wax dispersion: (15% by weight of wax) 33 parts Ethyl acetate 22 parts 5.3 Aluminum salt of 5,5-di-t-butyl 10 parts The oil phase of the above material composition was adjusted after confirming that the polyester resin was sufficiently dissolved. The oil phase was charged into a homomixer (Ace Homogenizer, manufactured by Nippon Seiki Co., Ltd.), and stirred at 15,000 rpm for 2 minutes to prepare a uniform oil phase. (D) The aqueous phase was prepared by the following procedure.

1. 1. Tricalcium phosphate: (average particle size 0.09 μm) 60 parts 40 parts of pure water The above-mentioned material was stirred with a ball mill for 4 days. The average particle size of tricalcium phosphate was measured using the above-mentioned laser diffraction / scattering particle size distribution analyzer LA-700 (Horiba, Ltd.) and found to be about 0.09 μm. On the other hand, a 2% by weight aqueous solution of polyvinyl alcohol (degree of polymerization 2000) was separately prepared. (E) The following materials were prepared as a toner production method.

1. 1. Oil phase produced by procedure (C): 60 parts 2. Calcium carbonate aqueous solution prepared by procedure (D): 10 parts Aqueous solution of polyvinyl alcohol prepared by procedure (D): 30 parts The above material was charged into a colloid mill (manufactured by Nippon Seiki Co., Ltd.), and emulsified for 20 minutes at 8000 revolutions per minute with a gap of 1.5 mm. Next, the above emulsion was put into a rotary evaporator, and the solvent was removed under reduced pressure of 30 mmHg at room temperature for 3 hours. Thereafter, 12N hydrochloric acid was added until the pH reached 2, and calcium carbonate was removed from the toner surface. Thereafter, centrifugal sedimentation was performed, and the supernatant was exchanged three times and washed, and then dried to take out the toner. The average particle size of the toner was 8.5 μm, and the GCD was 1.20 very good.
The wax content in the toner was 5.0% by weight. The hot offset temperature of the image was sufficiently high at 200 ° C., and the fixing strength was also good. The thermal stability index of the toner was 4.5%, which was very good. The developer was adjusted in the same manner as in Example 1, and the evaluation was performed on a real machine. The obtained image was a good one with high resolution. Further, continuous copying was performed for 30,000 sheets, but the image after 30,000 copies was good without any change from the initial state. The image was evaluated at high temperature and high humidity, but no image disorder was found. Table 4 shows the results. Example 8 Ion-exchanged water 710 was placed in a two-liter four-necked flask equipped with a high-speed stirrer TK homomixer.
A water-dispersible medium containing 60 parts by weight of calcium carbonate (Luminous: manufactured by Maruo Calcium Co., Ltd.) was prepared.

On the other hand, as the dispersoid, styrene monomer 165 parts n-butyl acrylate monomer 35 parts C.I. I. Pigment Blue 15: 3 14 parts Negative charge control agent (dialkyl salicylic acid compound) 2 parts Paraffin wax (melting point: 85 ° C., average particle size 0.85 μm) 15 parts After dispersing the above mixture for 3 hours using an attritor,
A polymerizable monomer composition (oil phase component) to which 10 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added was charged into the aqueous dispersion medium.

The stirring was continued at a liquid temperature of 80 ° C. for an hour. After the polymerization was completed, the slurry was cooled, dilute hydrochloric acid was added to remove the dispersion stabilizer, and after drying, a toner having an average particle size of 7.5 μm was obtained. Surface wax content 1.2% by weight, shape factor MLS
2 was 108. The wax content in the toner was 6.3% by weight. The hot offset temperature of the image was 180 ° C. and the fixing strength was good. The OHP transmittance was 81%. The developer was adjusted in the same manner as in Example 1, and the evaluation was performed on a real machine. The obtained image was excellent in high resolution. Further, continuous copying was performed for 30,000 sheets.
The image after 0000 sheets was good without any change from the initial state. The image was evaluated at high temperature and high humidity, but no image disorder was found. Table 4 shows the results. Example 9 A pigment dispersion was prepared in the following procedure.

1. 1. Polyester resin R-1 (described in Table 1): 45 parts (Tg; 63 ° C., softening point; 102 ° C., weight average molecular weight; 9000) 2. Copper phthalocyanine pigment: 50 parts (CI Pigment Blue 15: 3, Cyanine Blue 4933M; manufactured by Dainichi Seika) 3. 100 parts of ethyl acetate Charge control agent: (boron compound of salicylic acid) 5 parts Glass beads were added to the dispersion of the above-mentioned material composition, and the mixture was mounted on a sand mill disperser. While cooling around the dispersion container, the mixture was dispersed in a high-speed stirring mode for 3 hours to prepare a pigment dispersion having a pigment concentration of 10% by weight. Particles were produced in the same manner as in Example 1 except that the above dispersion was used. The average particle size of the toner was 7.0 μm, and the GSD was 1.30. The wax content in the toner was 4.8% by weight. An external additive was added thereto in the same manner as in Example 1 to obtain a toner. Image evaluation was carried out in the same manner except that the developing device shown in FIG. 4 was changed to the non-magnetic one-component developing device shown in FIG.

FIG. 5 is a schematic diagram showing the configuration of the non-magnetic one-component developing machine used in this embodiment. In the non-magnetic one-component developer 30, the toner is held in a toner reservoir 32, and a toner layer is formed on the developing roll 36 by a frictional force between the supply roll 34 and the developing roll 36. The toner layer is adjusted to a desired thickness by a regulating blade 38 and is supplied to a photoconductor (not shown).

As a result of forming an image by this method,
The transfer efficiency of each color from the photosensitive member 12 to the intermediate transfer member 18 is 9
The transfer efficiency from the intermediate transfer member 18 to the transfer material 24 is 98 to 99%, and the overall transfer efficiency is 96 to 98%.
High transfer efficiency. The obtained image was good with high resolution, and there was no offset to the transfer material. In addition, 5000 continuous copies were made, but 5000 copies were made.
The image after the printing was good without any change from the initial image. Further, image evaluation was performed at high temperature and high humidity, but no image disorder was found. (Comparative Example 1) Polypropylene wax (melting point 140 ° C, latent heat of fusion: 290 mJ) was used as the wax used in Example 1.
/ Mg) in the same manner as in Example 1 except that toner was used. The average particle size of the wax was measured to be about 3.9 μm. The average particle size of the toner is 8.3 μm,
GSD was 1.35. The wax content in the toner was 4.7% by weight. The hot offset temperature of the image occurred at 145 ° C., and the oilless fixability was insufficient. The thermal stability index of the toner was 8.4%. The developer was adjusted in the same manner as in Example 1, and the evaluation was performed on a real machine. O
The HP image was an image with a dark halftone. The obtained image was good in high resolution. Further, continuous copying was performed for 30,000 sheets. However, the image after 30,000 sheets was slightly reduced compared to the initial stage. Table 4 shows the results. (Comparative Example 2) The following materials were kneaded using a melt kneading method, pulverized and then classified to obtain a toner having a 7.8 µm GSD of 1.30. MLS2 152, surface wax content 54% by weight
Met. The wax content in the toner was 4.9% by weight.

1. 1. Polyester resin R-1: 90 parts (Tg; 65 ° C, softening point; 102 ° C, weight average molecular weight; 9000) Copper phthalocyanine pigment: 5 parts (Cyanine Blue 4933M; manufactured by Dainichi Seika Co., Ltd.) Paraffin wax: (melting point: 85 ° C., latent heat of fusion: 193 mJ / mg) 5 parts Hot offset of the image occurred at a temperature of 190 ° C., and the oilless fixability was sufficient, but the toner heat preservability index was 19%. It was very bad. The OHP image was an image having a dark halftone. The developer was adjusted in the same manner as in Example 1, and the evaluation was performed on an actual machine. The transfer efficiency from the photoreceptor 12 to the intermediate transfer member 18 is 85 to 87%, and the transfer efficiency from the intermediate transfer member 18 to the transfer material 24 is 90%.
It was as low as 78%. In the continuous evaluation, fogging occurred from about 1000 sheets, and the image quality deteriorated. After that, fog became more and more bad and the inside of the machine was severely stained with 5000 sheets. Further, the image was evaluated at high temperature and high humidity, but the image disorder became worse. Table 4 shows the results. Comparative Example 3 An amorphous toner was produced in the same manner as in Comparative Example 2 except that the amount of paraffin wax was changed to 1 part by weight. MLS2 was 153, and the amount of surface wax was 48% by weight. The wax content in the toner was 0.8% by weight. The oil-less fixability was sufficient, but the thermal stability index of the toner was very poor at 16%. The developer was adjusted in the same manner as in Example 1, and the evaluation was performed on a real machine. The transfer efficiency from the photosensitive member 12 to the intermediate transfer member 18 was 87 to 89%, and the transfer efficiency from the intermediate transfer member 18 to the transfer material 24 was 90%, which was low as 78 to 80% overall. In the continuous evaluation, fogging occurred from about 1000 sheets, and the image quality deteriorated. After that, fog became more and more bad and the inside of the machine was severely stained with 5000 sheets. Further, the image was evaluated at high temperature and high humidity, but the image disorder became worse. Table 4 shows the results. Comparative Example 4 An amorphous toner was produced by a pulverizing method in the same manner as in Comparative Example 2 except that the amount of paraffin wax was changed to 15 parts by weight. MLS2 was 153, and the amount of surface wax was 59% by weight. The wax content in the toner was 14.5% by weight. The toner heat preservability index was as very poor as 25%, and only images having very large transfer unevenness were obtained. In continuous evaluation of 500 sheets, many fusions to the photoreceptor occurred. Table 4 shows the results. (Comparative Example 5) 2.5 parts of a polyvalent isocyanate (Takenate D110N, manufactured by Takeda Pharmaceutical Co., Ltd.) and silyl isocyanate (SI310,
The same oil phase material (C) as in Example 1 was prepared except that 2.5 parts of Matsumoto Koshosha was added. Oil phase material (C)
Was converted into a toner in the same manner as described in (E) of Example 1 to prepare a capsule toner having a polyurea shell material layer provided on the toner surface. MLS2 is 110 and surface wax amount is 0.1.
It was 5% by weight. The wax content in the toner was 4.4% by weight.

As a result of evaluating the oilless fixing property, the offset start temperature was 145 ° C., which was insufficient. The OHP transmittance was as low as 78%, and the image produced by adjusting the developer in the same manner as in Example 1 had low surface gloss and low quality.
Table 4 shows the results.

[0098]

[Table 4]

As is clear from the above Examples, the toner of the present invention has a sufficient oil-less fixing property, and does not easily cause fusion or filming of the toner. Further, toner particles could be transferred from the photoreceptor and the intermediate transfer member at a high transfer rate, and a clear full-color image could be obtained. It was also found that the method was suitable for obtaining a color OHP image having excellent transparency. Further, from Example 9, it was found that a clear full-color image can be similarly obtained by changing the developing method according to the toner of the present invention. (Example 10) (A) Preparation of wax dispersion A pigment dispersion was prepared in the following procedure.

30 parts of paraffin wax (melting point 89 ° C.) and 250 parts of ethyl acetate are heated and dissolved, and the mixture is pressurized to a high pressure of 700 kg / cm ^{2 in} a pressure vessel, and then spouted to form a dispersion of the wax in ethyl acetate. Obtained. The average dispersion diameter of the wax is measured using a laser diffraction / scattering particle size distribution analyzer LA-
When measured with 700 (manufactured by Horiba, Ltd.), 0.7 μm
The number of pieces having a size of 5 μm or more was 0.5%. When the shape of the wax in the wax dispersion was observed with a scanning electron microscope (SEM) (FIG. 4), 90% of the flakes were flaky and had an average thickness of 0.1 mm.
The particles were 3 μm, the average of the vertical length was 0.9 μm, and the average of the horizontal length was 0.6 μm, and no particles of 5 μm or more were observed.
The measurement was obtained from an average of 20 wax particles in a SEM photograph. (B) Preparation of Oil Phase Polyester resin composed of bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, and succinic acid derivative (Tg 64 ° C., Tm 102
C., weight average molecular weight 9000) 100 parts by weight, C.I. After 4 parts by weight of I Pigment Blue 15: 3 and 80 parts by weight of ethyl acetate are dispersed in a ball mill for 10 hours, 36 parts by weight of an ethyl acetate dispersion of wax is added, and the mixture is stirred well until uniform to prepare an oil phase component. did. (C) Preparation of aqueous phase 60 parts by weight of calcium carbonate and 40 parts by weight of water were dispersed in a ball mill for 10 hours, and then 7 parts by weight of a calcium carbonate dispersion and a 2% aqueous solution of cellogen BS-H (manufactured by Daiichi Kogyo Seiyaku) 100
The weight part was put in a cooking mixer MX-915C (manufactured by Matsushita Electric Industrial Co., Ltd.) and mixed for 5 minutes to prepare an aqueous phase liquid. (D) Toner Production Method 100 parts by weight of the oil phase liquid was added to this aqueous phase liquid, mixed for 6 minutes with a cooking mixer, and heated in a water bath at 40 ° C. to remove the solvent. After 100 parts by weight of 6N hydrochloric acid was added to remove calcium carbonate, the solid was washed with water and dried to obtain a solid toner having an average particle diameter of 7.1 μm. Looking at the SEM photograph, the shape was almost spherical. To confirm the shape of the wax in the toner, the toner was dissolved in toluene, and the shape of the insoluble matter filtered was determined in the same manner as the measurement of the shape of the wax in the dispersion.
Observation with an EM photograph showed that 85% was flaky and had an average thickness of 0.41 μm, an average vertical length of 1.0 μm, and an average horizontal length of 0.7 μm. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was largely dispersed inside the toner, and the amount of wax exposure on the surface of the toner particles was 4%. The wax content in the toner was 3.1% by weight. (E) Adjustment of developer and evaluation with actual machine A-color 935 (manufactured by Fuji Xerox Co., Ltd.) was prepared by mixing 1 part by weight of silica R972 (manufactured by Nippon Aerosil Co., Ltd.) with 100 parts by weight of toner in a sample mill for 1 minute. The image was formed without fixing fuser oil and evaluated, and the evaluation results are shown in Table 5. The following evaluation methods are suitable, and the image quality is as follows:
The image density, the presence or absence of fog, and the fixability to paper and OHP were visually determined. The offset was visually checked for toner adhesion to the fixing roll at the initial stage and after copying 1000 sheets. The light transmittance of the OHP was measured by measuring the light transmittance at a wavelength at which no colorant was absorbed after the solid image was fixed on the OHP. The wax diameter in the toner was determined from an average value of ten horizontal diameters randomly selected from a TEM photograph of the cross section of the toner. For the storage stability, the presence or absence of aggregation after the toner was left at 50 ° C. for 3 hours was examined. The transferability was determined by visually checking the presence or absence of toner remaining on the surface of the photoconductor immediately after the transfer to paper. (Example 11) Microcrystalline wax (melting point 8)
(4 ° C.) 30 parts by weight of heat were dissolved in 250 parts by weight of toluene, and then pressure was applied to a high pressure state of 500 kg / cm ^{2 in} a pressure vessel, followed by ejection to obtain a wax ethyl acetate dispersion. The average dispersion diameter of the wax was 0.9 μm when measured with a laser diffraction / scattering particle size distribution analyzer LA-700 (manufactured by Horiba, Ltd.).
2%. When the shape of the wax in the wax dispersion was observed with a scanning electron microscope (SEM), 85% of the flakes were in the form of flakes, the average thickness was 0.3 μm, and the average vertical length was 1.0 μm.
m, the average of the horizontal length was 0.5 μm, and the number of particles having a size of 5 μm or more was 5%.

Polyester resin comprising bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, and succinic acid derivative (Tg 64 ° C.,
Tm: 102 ° C., weight average molecular weight: 9000) 100 parts by weight, C.I. After 3 parts by weight of I Pigment Red 57 and 100 parts by weight of ethyl acetate were dispersed in a sand mill for 5 hours, 36 parts by weight of an ethyl acetate dispersion of wax was added, and the mixture was thoroughly stirred until it became uniform to prepare an oil phase component.

60 parts by weight of calcium carbonate and 40 parts by weight of water were dispersed in a ball mill for 10 hours, and then 6 parts by weight of a calcium carbonate dispersion and 2% of cellogen BS-H (Daiichi Kogyo Seiyaku) were prepared.
100 parts by weight of aqueous solution is used as a cooking mixer MX-915
C (Matsushita Electric) and mixed for 5 minutes to prepare an aqueous phase liquid. To this aqueous phase liquid, add 50 parts by weight of the oil phase liquid,
After mixing with a cooking mixer for 6 minutes, the mixture was heated in a 70 ° C. water bath to remove the solvent. 100 parts by weight of 6N hydrochloric acid was added to remove calcium carbonate, followed by washing with water and drying to obtain a solid toner having an average particle diameter of 6.1 μm. Looking at the SEM photograph, the shape is almost spherical. Observation with a SEM photograph to confirm the shape of the wax in the wax dispersion showed that 85% of the flakes were flaky and had an average thickness of 0.3 μm, an average length of 1.0 μm, and an average width. It was 0.7 μm. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was largely dispersed inside the toner, and the amount of the wax exposed on the surface of the toner particles was 5%. The wax content in the toner was 3.0% by weight.

An external silica toner obtained by mixing 1 part by weight of silica R972 (manufactured by Nippon Aerosil Co., Ltd.) with 100 parts by weight of a toner in a sample mill for 1 minute was used in Example with A-color 935 (manufactured by Fuji Xerox Co., Ltd.) without fixing fuser oil. Evaluation was performed in the same manner as in No. 10, and the evaluation results are shown in Table 5. Example 12 After heating and dissolving 30 parts by weight of Fischer-Tropsch wax (melting point 98 ° C.) in 250 parts by weight of toluene, pressure was applied to a high pressure state of 700 kg / cm ^{2 in} a pressure vessel, and then the wax was ejected. Was obtained. The average dispersion diameter of wax is 0.8 μm and 5 μm
The number of m or more was 2% (measured with a laser diffraction / scattering particle size distribution analyzer LA-700 (manufactured by Horiba, Ltd.)). Scanning electron microscope (S)
When observed by EM), 90% of the flakes were in the form of flakes, the average thickness was 0.3 μm, the average vertical length was 0.9 μm, the average horizontal length was 0.6 μm, and the number of particles of 5 μm or more was 5 μm. %Met.

Styrene-n-butyl acrylate 80:
20 (weight average molecular weight: 200000) copolymer resin 1
00 parts by weight, C.I. After 6 parts by weight of I Pigment Yellow 17 and 1000 parts by weight of toluene were dispersed in a sand mill for 5 hours, 72 parts by weight of a toluene dispersion of wax was added, and the mixture was stirred well until uniform to prepare an oil phase component.

After 60 parts by weight of calcium carbonate and 40 parts by weight of water were dispersed in a ball mill for 10 hours, 6 parts by weight of a calcium carbonate dispersion and 2% of cellogen BS-H (Daiichi Kogyo Seiyaku) were prepared.
100 parts by weight of the aqueous solution is placed in a tabletop colloid mill (manufactured by Nippon Seiki Seisakusho), and mixed at 5000 rpm for 5 minutes to prepare an aqueous phase liquid. 50 parts by weight of the oil phase liquid was added to the aqueous phase liquid, mixed at 8000 rpm for 20 minutes, and the solvent was removed under reduced pressure in a water bath at 25 ° C. After adding 100 parts by weight of 6N hydrochloric acid to remove calcium carbonate, washing with water and drying were performed to obtain a solid toner having an average particle diameter of 7.4 μm. Looking at the SEM photograph, the shape was almost spherical. When the shape of the wax in the wax dispersion was observed with a SEM photograph, 85% of the flakes were flaky and had an average thickness of 0.3 μm and an average vertical length of 1.0%.
μm, the average of the horizontal length was 0.6 μm, and the number of particles of 5 μm or more was 5%. In a transmission electron microscope (TEM) photograph of the toner cross section, the wax was largely dispersed inside the toner, and the amount of wax exposure on the surface of the toner particles was 3%. The wax content in the toner was 3.0% by weight.

An external silica-added toner prepared by mixing 1 part by weight of silica R972 (manufactured by Nippon Aerosil Co., Ltd.) with 100 parts by weight of a toner in a sample mill for 1 minute was used in Example with A-color 935 (manufactured by Fuji Xerox) without fixing fuser oil. Evaluation was performed in the same manner as in No. 10, and the evaluation results are shown in Table 5. (Example 13) Paraffin wax (melting point 89 ° C) 30
After heating and dissolving parts by weight in 250 parts by weight of ethyl acetate,
After pressure was applied to a high pressure state of 700 kg / cm ^{2 in} a pressure vessel, it was ejected to obtain a wax ethyl acetate dispersion. The average dispersion diameter of the wax was 0.8 μm, and the number of particles having a diameter of 5 μm or more was 2% (measured by a laser diffraction / scattering particle size distribution analyzer LA-700 (manufactured by Horiba, Ltd.)). Scanning electron microscopy (SEM) of wax shape in wax dispersion
As a result, 90% of the flakes were in the form of flakes and the average thickness was 0.3 μm.
m, the average of the vertical length was 0.9 μm, the average of the horizontal length was 0.6 μm, and the number of particles of 5 μm or more was 5%.

Styrene-n-butyl acrylate 80:
20 (weight average molecular weight: 200000) copolymer resin 1
After 00 parts by weight, 5 parts by weight of carbon black and 1000 parts by weight of ethyl acetate were dispersed in a sand mill for 5 hours, 42 parts by weight of an ethyl acetate dispersion of wax was added, and the mixture was stirred well until uniform to prepare an oil phase component. did.

After 60 parts by weight of calcium carbonate and 40 parts by weight of water were dispersed in a ball mill for 10 hours, 6 parts by weight of a calcium carbonate dispersion and 2% of cellogen BS-H (Daiichi Kogyo Seiyaku) were prepared.
100 parts by weight of the aqueous solution was placed in a tabletop colloid mill (manufactured by Nippon Seiki Seisakusho) and mixed at 5000 rpm for 5 minutes to prepare an aqueous phase liquid. 50 parts by weight of the oil phase liquid was added to the aqueous phase liquid, mixed at 8000 rpm for 20 minutes, and the solvent was removed under reduced pressure in a water bath at 25 ° C. After adding 100 parts by weight of 6N hydrochloric acid to remove calcium carbonate, washing with water and drying were performed to obtain a solid toner having an average particle diameter of 7.4 μm. Looking at the SEM photograph, the shape is almost spherical. When the shape of the wax in the wax dispersion was observed with a SEM photograph, 890 was flaky and had an average thickness of 0.3 μm and an average vertical length of 1.0.
μm, the average of the horizontal length was 0.6 μm, and the number of particles of 5 μm or more was 5%. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was largely dispersed inside the toner, and the amount of wax exposure on the surface of the toner particles was 7%. The wax content in the toner was 3.3% by weight.

A silica external additive toner obtained by mixing 1 part by weight of silica R972 (manufactured by Nippon Aerosil Co., Ltd.) with 100 parts by weight of a toner in a sample mill for 1 minute was used in Example with A-color 935 (manufactured by Fuji Xerox Co., Ltd.) without fixing fuser oil. Evaluation was performed in the same manner as in No. 10, and the evaluation results are shown in Table 5. (Comparative Example 6) Styrene-n-butyl acrylate 80:
20 (weight average molecular weight: 200000) copolymer resin, 100 parts by weight, 3 parts by weight of CI Pigment Red 57, and 3 parts by weight of paraffin wax (melting point: 89 ° C.) were added, kneaded and pulverized by a kneader, and then classified. Average particle size 7.8 μm
Was obtained. Observation of the wax shape with a SEM photograph revealed that 95% of the wax was substantially spherical, and the average particle size was 0.9 μm.
And no particles of 5 μm or more were observed. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was partially exposed on the surface of the toner particles. The amount of surface wax determined by ESCA was 32%. The wax content in the toner was 2.8% by weight.

A silica-added toner prepared by mixing 1 part by weight of silica R972 (manufactured by Nippon Aerosil Co., Ltd.) with 100 parts by weight of a toner in a sample mill for 1 minute using A-co1or935 (manufactured by Fuji Xerox Co., Ltd.) without fixing fuser oil. Evaluation was performed in the same manner as in No. 10, and the evaluation results are shown in Table 5. (Comparative Example 7) A solid toner having an average particle size of 8.1 µm was obtained in the same manner as in Comparative Example 2, except that 3 parts by weight of the wax of Comparative Example 6 was changed to 15 parts by weight. SEM wax shape
Observation with a photograph revealed that 90% was almost spherical and averaged 1.0%
μm, and particles of 5 μm or more were not observed. In a transmission electron microscope (TEM) photograph of the cross section of the toner, the wax was partially exposed on the surface of the toner particles. ESCA
Was 46%. The wax content in the toner was 12.5% by weight.

An external silica-added toner obtained by mixing 1 part by weight of silica R972 (manufactured by Nippon Aerosil Co., Ltd.) with 100 parts by weight of a toner in a sample mill for 1 minute was used for the A-co1or935 (manufactured by Fuji Xerox Co., Ltd.) without fixing fuser oil. Evaluation was performed in the same manner as in No. 10, and the evaluation results are shown in Table 5.

[0112]

[Table 5]

As is clear from these Examples and Comparative Examples, the toner prepared by dispersing the flaky wax has good storage stability and transferability.
After the copying, image quality was reduced.

[0114]

The toner for an electrostatic latent image developer of the present invention and the electrostatic latent image developer containing the toner do not need to supply oil to a fixing system, and use oilless fixing properties and wax. The effect of achieving both the powder characteristics of the toner, the filming property, and the high transfer property required for a color image at a high level is exhibited, which is advantageous for designing an inexpensive copying machine or printer. Further, according to the method for producing the toner of the present invention, this novel toner having excellent characteristics can be produced by a simple method. According to the image forming method of the present invention, the image quality is high and the OHP transmission is high. A good image can be formed.

[Brief description of the drawings]

FIG. 1 is a wax particle model diagram showing the vertical, horizontal, and thickness directions of a wax particle.

FIG. 2 is a schematic cross-sectional view showing a wax fine dispersion device which has a gap at a predetermined pressure or higher and ejects a mixed liquid.

FIG. 3 is a schematic sectional view showing a wax fine dispersion device having a fine opening (nozzle).

FIG. 4 is a schematic diagram illustrating a configuration of an image forming apparatus used in the image forming method according to the first exemplary embodiment.

FIG. 5 is a schematic diagram illustrating a configuration of a non-magnetic one-component developing machine used in an image forming method according to a ninth embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Image forming apparatus 12 Photoreceptor (electrostatic latent image carrier) 14 Charger 15 Exposure apparatus 16c, 16m, 16y, 16b Four-color developing device 18 Intermediate transfer body 20 Cleaning means 22 Transfer charger 24 Transfer material 26 Heat fixing roll (Heating roll) 28 Pressure roll 30 Non-magnetic one-component developing machine 32 Toner reservoir 34 Supply roll 36 Developing roll 38 Regulator blade 40, 48 Fine wax dispersion device

Continued on the front page (72) Inventor Isamu Suzuki 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Xerox Co., Ltd.

Claims (20)

[Claims] 1. A toner for an electrostatic latent image developer comprising a binder resin and a colorant, wherein the toner contains 0.1 to 40% by weight of wax and 1 to 10% by weight of wax exposed on the toner surface. % And a number average dispersion diameter of the wax is 0.1 to 2 μm. 2. The toner for an electrostatic latent image developer according to claim 1, wherein the wax has a flaky shape. 3. The method according to claim 1, wherein the wax has a thickness of 0.5 μm based on the total number of wax particles.
m or less, and the ratio of the flaky wax particles whose maximum length in the vertical direction is twice or more the thickness and whose maximum length in the horizontal direction is 1.5 times or more the thickness is 75% or more. 3. The toner for a developer for an electrostatic latent image according to claim 2, wherein: 4. The method according to claim 1, wherein the maximum length of the wax dispersion unit in the vertical direction is 5 μm with respect to the total number of the wax particles.
3. The toner for an electrostatic latent image developer according to claim 2, wherein the number of toner particles having a particle size of m or more is 10% or less, and the average length of the flaky wax particles is 1 μm or less. 5. The toner for an electrostatic latent image developer according to claim 1, wherein the melting point of the wax is 110 ° C. or less. 6. The latent heat of melting of the wax is 230 m
2. The toner for an electrostatic latent image developer according to claim 1, wherein the amount is J / mg or less. 7. The toner according to claim 1, wherein the wax is a petroleum wax or a synthetic wax. 8. The toner for an electrostatic latent image developer according to claim 1, wherein the value of the shape factor MLS2 of the toner particles is in a range of 100 to 140. 9. A two-component developer comprising a carrier and a toner, wherein the toner contains 0.1 to 40% by weight of wax, and 1 to 10% by weight of wax exposed on the surface of the toner.
An electrostatic latent image developer characterized in that the wax has a number average dispersion diameter of 0.1 to 2 μm. 10. The electrostatic latent image developer according to claim 9, wherein the melting point of the wax is 110 ° C. or less. 11. The electrostatic latent image developer according to claim 9, wherein the wax has a flaky shape. 12. A method for producing a toner for an electrostatic latent image developer containing at least a resin, a colorant, and a wax,
A step of dissolving or dispersing the raw materials of the resin, the colorant, and the wax in an organic solvent to form an oil phase component, and a step of granulating the oil phase component in an aqueous solvent, A method for producing a toner for an electrostatic latent image developer, wherein the number average dispersion diameter of the wax contained in the formed toner is 0.1 to 2 μm. 13. A method for producing a toner for an electrostatic latent image developer containing at least a resin, a colorant, and a wax, wherein the raw materials of the resin, the colorant, and the wax are dissolved or dispersed in an organic solvent to obtain an oil. A step of forming a phase component, a step of granulating the oil phase component in an aqueous solvent, and a step of suspending and polymerizing the particles formed by the granulating step. A method for producing a toner for an electrostatic latent image developer, wherein the number average dispersion diameter of wax contained in the toner is 0.1 to 2 μm. 14. The method for producing a toner for an electrostatic latent image developer according to claim 12, wherein the wax is produced by pulverizing the wax in an organic solvent. 15. Before the step of forming the oil phase component,
Dissolving or dispersing the wax in an organic solvent,
Cooling the organic solvent to precipitate wax to obtain fine wax particles.
A method for producing the toner for an electrostatic latent image developer according to the above. 16. Before the step of forming the oil phase component,
13. The method for producing a toner for an electrostatic latent image developer according to claim 12, comprising a step of evaporating the wax into a gas phase and a step of coagulating the wax to obtain fine wax particles. 17. The toner for an electrostatic latent image developer according to claim 12, wherein an inorganic dispersion stabilizer and / or an organic dispersion stabilizer having a hydrophilic colloid is added to the aqueous solvent. Production method. 18. The method according to claim 12, further comprising an acid washing step of adding an acid to the formed toner to make the dispersion stabilizer remaining on the toner water-soluble and removing the dispersion stabilizer from the toner surface. A method for producing a toner for an electrostatic latent image developer. 19. The toner for an electrostatic latent image developer according to claim 12, further comprising an alkali washing step of adding an alkali to the formed toner to remove wax remaining on the toner. Production method. 20. An image forming method, comprising: forming a latent image on an image carrier, developing the latent image using a developer, and transferring the formed toner image onto a transfer member. A toner containing a binder resin, a colorant, and a wax as the developer, wherein the toner contains 0.1 to 40% by weight of the wax, and one of the wax exposed on the toner surface is a toner.
-10% by weight, and the wax has a number average dispersion diameter of 0.1%.
An image forming method using an electrostatic latent image developer containing a toner having a thickness of 1 to 2 μm.